WO2015175172A1 - Agents de soutènement en céramique - Google Patents

Agents de soutènement en céramique Download PDF

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Publication number
WO2015175172A1
WO2015175172A1 PCT/US2015/026833 US2015026833W WO2015175172A1 WO 2015175172 A1 WO2015175172 A1 WO 2015175172A1 US 2015026833 W US2015026833 W US 2015026833W WO 2015175172 A1 WO2015175172 A1 WO 2015175172A1
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Prior art keywords
weight percent
sintered
generally spherical
particles
content
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PCT/US2015/026833
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English (en)
Inventor
Frank O'brien
Chris Heller
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Shamrock Group
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Priority claimed from US14/275,226 external-priority patent/US9434873B2/en
Application filed by Shamrock Group filed Critical Shamrock Group
Priority to CA2949072A priority Critical patent/CA2949072A1/fr
Publication of WO2015175172A1 publication Critical patent/WO2015175172A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/80—Compositions for reinforcing fractures, e.g. compositions of proppants used to keep the fractures open
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B33/00—Clay-wares
    • C—CHEMISTRY; METALLURGY
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C04B35/19—Alkali metal aluminosilicates, e.g. spodumene
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH OR ROCK DRILLING; MINING
    • E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
    • E21B43/25—Methods for stimulating production
    • E21B43/26—Methods for stimulating production by forming crevices or fractures
    • E21B43/267—Methods for stimulating production by forming crevices or fractures reinforcing fractures by propping
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/528—Spheres
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    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Definitions

  • the claimed technology relates generally to small, generally spherical ceramic bodies and, more particularly, to alumina-silicate proppant bodies for use in fracturing subterranean geological formations.
  • Hydraulic fracturing is a technique for increasing the output and productivity of oil and gas wells by cracking the geological formation surrounding and defining an oil and/or gas reserve to create pathways through which the entrapped oil and/or gas may more easily flow for extraction.
  • a highly pressurized fluid is injected into an existing well bore at a sufficiently high rate of flow to put sufficient stress on the geological formation to induce fracturing thereof, thus creating a network of cracks in the rock defining the oil and gas reservoir.
  • a fluid containing a vast amount of small particulate propping agents, or proppants is introduced into the crack network such that the proppants will become positioned in the newly-opened fissures to prevent their closure due to geological forces. In other words, the proppants literally "prop" the cracks open.
  • the proppants are typically formed to have sufficient mechanical strength to hold the cracks open against the dynamic geological forces that would otherwise operate to close or distort them. Typically, these geological forces increase with the depth of the well. Also, proppants are typically made to be somewhat fluid permeable and/or conductive, such that even when present in aggregate, they do not substantially obstruct the flow of oil and/or gas desired to be extracted from the well. Typically, propping agents have been made stronger through densification or by increasing the alumina content thereof. However, denser, heavier proppants are harder to pump, more expensive to transport, and are less permeable than lighter, more porous agents.
  • proppants are inexpensive to produce, since it takes a great volume of proppants to hold open cracks in even a relatively small well.
  • Sand is cheap and plentiful and is often selected as an advantageous propping agent for maintaining the cracks formed in wells and geological formations experiencing relatively low closure forces (i.e., 4,000 psi or less).
  • the strength of the sand may be extended to withstand closure forces of 8000 psi or more through such sorting processes as screening, sizing and shaping the sand.
  • the sand proppant performance drops off dramatically as the closure forces increase, such that even highly processed and selected sand is inadequate under closure forces much exceeding 10,000 psi.
  • sand tends to be nonporous, and as such is less than ideal from a permeability standpoint.
  • sorting and processing steps add expense, thus detracting from one of the main characteristics, low expense, making sand attractive in the first place.
  • high-alumina aluminosilicate compositions such as bauxite with an alumina content in the 75-90% range, offer sufficient strength to function as proppants under relatively high closure forces and at relatively great well depths.
  • these high-alumina proppants likewise have high densities/ apparent specific gravities approaching or exceeding 3.5 g/cc, and thus add the requirement of high viscosity pumping fluids and/or high pumping rates to prevent them from settling out during the injection process.
  • Increased fluid viscosity and the requisite high pumping rates cost precision and control of the injection operation, thus making fracture control and high conductivity fractures more difficult to achieve and maintain.
  • the high-alumina proppants tend to be more abrasive, and thus speed the wear of the pumping and fluid transport equipment.
  • sintered high-alumina compositions are relatively expensive, often priced ten to fifteen times that of sand.
  • Intermediate density proppants defined as those having an apparent specific gravity in the 3.1 to 3.4 g/cc range, have been developed to provide sufficient strength to keep cracks open at well depths of from about 8,000 to about 12,000 feet. In these materials, lower density is achieved primarily by reduction of the alumina content to about 75%. Proppants having even lower densities, such as around 3.0 g/cc, have been formed from kaolin clay precursors and are characterized by an alumina content of about 50%. These low density proppants are typically intended for use at well depths up to about 8,000 feet.
  • An even lower density proppant has been developed having an alumina content of from 25% to 40% and an apparent specific gravity of from 2.20 to 2.60 g/cc. While the reduced density allows for the use of less viscous pumping fluid and lower pumping rates (which are both desirable for prolonging equipment life and thus reducing repair and replacement costs), the tradeoff is in proppant strength. Lowering the alumina content of the material generally results in a lower density proppant with corresponding lower strength, since the higher silica content results in significant loss of strength.
  • the claimed novel technology relates to an improved formulation for ceramic proppant bodies characterized by a relatively low alumina content.
  • One object is to provide an improved ceramic proppant formulation.
  • the claimed technology relates to a light weight sintered ceramic material of intermediate strength, such as a propping agent or proppant useful in the hydraulic fracturing of subterranean geological formations surrounding and defining oil wells, gas wells and similar boreholes.
  • a propping agent or proppant useful in the hydraulic fracturing of subterranean geological formations surrounding and defining oil wells, gas wells and similar boreholes.
  • the sintered ceramic material is typically formed as solid, substantially spherical particles or pellets and is typically characterized as having a silica content between about 52 and about 58 weight percent, an alumina content of between about 32 and about 39 weight percent, an apparent specific gravity of between about 2.61 and 2.69 (more typically between about 2.63 and 2.65), a bulk density of between about 1.41 and about 1.65 grams per cubic centimeter (more typically a loose fill density of between about 1.45 and 1.55, or between about 1.54 and about 1.61 g/cc), Krumbein sphericity of at least about 0.7 (more typically at least about 0.8 and still more typically at least about 0.9), a mechanical crush strength such that no more than 10% of a test population are crushed at 7500 PSl (more typically no more than 5% at 7500 PSl and/or no more than 10% at 8000 PSl), and an ambient temperature permeability of at least about 100,000 millidarcies at 8,000 psi.
  • the aluminosilicate proppant particles typically have a silica (Si0 2 ) content of between about 54 and about 55 weight percent, an alumina (Al 2 0 3 ) content of between 30 and about 36 weight percent.
  • Typical proppant particle composition ranges (in weight percents) are as follows:
  • proppants typically have a specific gravity of between about 2.61 and about 2.69 and more typically between about 2.63 and about 2.65.
  • the proppants typically have a bulk density of between about 1.41 and about 1.65, and more typically between about 1.45 and about 1.55 gm/cc.
  • the propping agent particles are made from high-iron aluminosilicate materials or fireclay typically found deposited in and around St. Louis, High Hill and Mexico Missouri (i.e., Missouri fireclay). Similar mineral formations may also be found in such places as Ohio, Kentucky, Pennsylvania, certain parts of Europe and the like.
  • Missouri fireclay is a relatively high iron-content bauxite or bauxitic material.
  • the Missouri fireclay will be blended with at least some (typically, about 5 weight percent or more) high iron aluminosilicate, a high iron aluminosilicate source, or similar mineral compositions.
  • a small amount (typically around 5 weight percent) crush strength enhancer material may be added to the Missouri fireclay to increase the strength of the proppants produced therefrom.
  • the crush strength enhancer is typically a material such as nepheline syenite, fused bauxite dust, wollastonite, talc, feldspar, rutile, bentonite, ball clay, fireclay or the like, which act to increase the strength of the aluminosilicate proppants particles without substantially altering their density, specific gravity, conductivity and the like.
  • small additions of crush strength enhancers such as these operate to impede cristobalite formation during the sintering of the proppant particles, thus increasing their crush strength.
  • the propping agent particles are typically prepared from a dry mixed precursor including the Missouri fireclay material, any additional clays, any strength enhancing additives, and a suitable binder to yield a composition within the ranges outlined above.
  • the precursors may be mixed as an aqueous suspension or the like.
  • the dry mixed precursor is typically a substantially homogeneous mixture, and yields green and, later, fired proppants having substantially homogeneous compositions with the component oxides homogeneously distributed therein. The mixture is then granulated through mixture-intensive shaping into generally spherical particles.
  • the generally spherical particles are typically larger than the desired size of the final proppant particles, to allow for shrinkage to occur during the firing process (i.e., the final proppant size is typically targeted to a convenient size range, such as 16/30 mesh, 20/40 mesh, 40/80 mesh, or the like) .
  • Those fractions of undesired sizes, such as undersized and oversized fractions, are typically recycled into the layer of fluidized particles.
  • the non-recycled fractions are then typically dried, calcined and sintered. Sintering is typically accomplished at a temperature of between about 2345 and about 2450 degrees Fahrenheit (or between about 1285 and about 1327 degrees Celsius) to yield sintered proppants.
  • the as-sintered proppants typically have a specific gravity of between about 2.61 and about 2.69, more typically about 2.63 to about 2.65; this relatively low specific gravity allows for easier and less destructive pumping of a fluid containing the proppants for injection into crack formations. More typically, the proppants are characterized by a Krumbein sphericity of about 0.7 or greater. Still more typically, the proppants have a Krumbein sphericity of at least about 0.8; yet more typically, the proppants have a Krumbein sphericity of at least about 0.9.
  • the propping agents have sufficient mechanical strength such that 80% of a sample may withstand crushing forces of 7500 psi; more typically, at least about 90% survive. Still more typically, the propping agents have sufficient mechanical strength such that 90% of a sample may withstand crushing forces of 8000 psi and/or 95% of the sample may withstand a crushing load of 7500 psi.
  • the proppants are typically characterized by a 20% crush at 7500 psi; more typically a 10% crush at 7500 psi; and still more typically by a 10 percent crush at 8000 psi and/or a 5% crush at 7500 psi..
  • Green strength may be increased through the addition of starches, swelling clay, KCI, NaOH, NH 4 CI, PVA, or other binders.
  • This material is generally formed through mixer granulation techniques to yield a small, generally spherical pellet.
  • the pellets are typically screened and extracted and sized in target, oversized and undersized fractions or ranges.
  • the oversized fractions may be ground down to size, such as in a grinding unit, while the undersized fractions may be recycled or extracted for other uses.
  • the remaining material at target size may be calcined to remove excess moisture and volatilize unwanted organics.
  • the remaining material may then be formed into any desired shapes and sizes, and/or merely sintered in a rotary kiln at a temperature of between about 1285 and 1325 degrees Celsius for 30 minutes or less.
  • the sintered substantially spherical particles are characterized by a substantially homogeneouos distribution of silica and alumina therethrough.
  • the sintered particles are then subjected to a further sieving operation to further control the desired particle size.
  • sintered proppant particles of the above compositional range are fluidically injected into precracked geological formations surrounding and defining oil and/or gas wells.
  • the proppants become positioned in the cracks in sufficiently high numbers and concentrations to wedge or prop the cracks open, resisting geological forces arising that would otherwise urge the cracks shut.
  • the proppants provide a propping layer that is sufficiently fluid permeable/conductive that fluids such as oil and/or gas may readily escape through the cracks and be extracted from the well.
  • the proppants may be prepared and formed via any convenient alternate aqueous process or any convenient dry or powder process.
  • a 20/40 mesh proppant sample was prepared and crush tested.
  • the composition of the proppant sample was analyzed via inductively coupled plasma-atomic emission spectroscopy and was found to have the following composition, expressed in oxide form:
  • the specific gravity of the sample was measured to be 2.63 and the bulk density was measured to be 1.49. Portions of the sample were extracted for crush testing at various pressures. The crush test results are as follows:
  • Example 2 The sample had a crush at 7500 PSl of less than 5% and a crush at 10000 PSl of about 10%.
  • Example 2 The sample had a crush at 7500 PSl of less than 5% and a crush at 10000 PSl of about 10%.
  • Example 1 The sample of Example 1 was subjected to roundness and sphericity analysis.
  • Roundness is essentially a measure of the degree of abrasion of particles and may be expressed as the ratio of the average radius of curvature of the edges or corners of a particle to the radius of curvature of the maximum inscribed sphere.
  • Sphericity while similar in concept to roundness, is a measure of how close in overall shape a particle is to a sphere, and may be taken as the ratio of the surface area of an idealized sphere to the surface area of a particle of the same volume. Sphericity is often visually measured, such as on the Krumbein scale.
  • a 20/40 mesh proppant sample was prepared and crush tested.
  • the composition of the proppant sample was analyzed via inductively coupled plasma-atomic emission spectroscopy and was found to have the following composition, expressed in oxide form:
  • the sample had a specific gravity of 2.63 and a bulk density of 1.49.
  • the acid solubility of the sample was measured to be 4.0% ⁇ 0.0 in accordance with ISO 13503-2, section 8 procedures using 60% HF as a source.

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Abstract

On décrit un corps en céramique fritté, généralement sphérique, qui présente une teneur en alumine d'environ 52 à environ 55 pour cent en poids répartie de manière sensiblement homogène dans tout le corps; une teneur en silice d'environ 32 à environ 38 pour cent en poids répartie de manière sensiblement homogène dans tout le corps; une gravité spécifique apparente d'environ 2,61 à environ 2,65; et une densité apparente d'environ 1,45 à environ 1,56 grammes par centimètre cube.
PCT/US2015/026833 2014-05-12 2015-04-21 Agents de soutènement en céramique WO2015175172A1 (fr)

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US14/275,226 US9434873B2 (en) 2011-01-07 2014-05-12 Ceramic proppants
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467414A (zh) * 2018-10-29 2019-03-15 裴泽民 一种抗压裂陶粒支撑剂的制备方法

Citations (3)

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Publication number Priority date Publication date Assignee Title
US4427068A (en) * 1982-02-09 1984-01-24 Kennecott Corporation Sintered spherical pellets containing clay as a major component useful for gas and oil well proppants
US4555493A (en) * 1983-12-07 1985-11-26 Reynolds Metals Company Aluminosilicate ceramic proppant for gas and oil well fracturing and method of forming same
US20130255945A1 (en) * 2011-01-07 2013-10-03 Frank O'Brien Ceramic proppants

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427068A (en) * 1982-02-09 1984-01-24 Kennecott Corporation Sintered spherical pellets containing clay as a major component useful for gas and oil well proppants
US4427068B1 (fr) * 1982-02-09 1992-03-24 Carbo Ceramics Inc
US4555493A (en) * 1983-12-07 1985-11-26 Reynolds Metals Company Aluminosilicate ceramic proppant for gas and oil well fracturing and method of forming same
US20130255945A1 (en) * 2011-01-07 2013-10-03 Frank O'Brien Ceramic proppants

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467414A (zh) * 2018-10-29 2019-03-15 裴泽民 一种抗压裂陶粒支撑剂的制备方法

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